Fiber-reactive azo dyes, preparation thereof and use thereof

ABSTRACT

Reactive dyes as per the hereinbelow indicated and defined general formula (I)  
                 
 
where D 1  and D 2 , R and R* and also M are each as defined in claim  1,  processes for their preparation and their use for dyeing or printing hydroxyl- and/or carboxamido-containing fiber material.

This invention relates to the field of fiber-reactive azo dyes.

Fiber-reactive azo dye mixtures and their use for dyeing hydroxyl-and/or carboxamido containing material in yellowish to brownish red huesare known for example from the documents JP 8060017 WO 00/06652 and DE19600765 A1. However, these have certain performance defects, forexample an excessive dependence of the color yield on changing dyeingparameters in the dyeing operation, or an insufficient or unlevel colorbuild-up on cotton (good color build-up follows from the ability of thedye to produce a correspondingly stronger dyeing from an increasedconcentration of the dye in the dyebath). Possible consequences of thesedefects are poor reproducibilities for the dyeings which are obtainable,which ultimately compromises the economics of the dyeing operation.Consequently, there continues to be a demand for novel reactive dyeshaving improved properties, such as high substantivity combined withgood wash-off of unfixed portions. They shall moreover provide gooddyeing yields and possess high reactivity and they shall moreparticularly provide dyeings having high degrees of fixation.

The present invention, then, provides dyes which possess theseabove-described properties to a high degree. The novel dye mixturesshould be notable in particular for high fixation yields and readywash-off of portions not fixed on the fiber. In addition, the dyeingsshould possess good general fastnesses, such as for example highlightfastness and very good wetfastnesses.

The present invention accordingly provides dyes of the hereinbelowindicated and defined general formula (I)

where

-   -   D¹ and D² are independently a group of the general formula (1)    -    where        -   R¹ and R² are independently hydrogen, (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro,            amido, ureido or halogen; and        -   X¹ is hydrogen or a group of the formula —SO₂-Z, where            -   Z is —CH═CH₂, —CH₂CH₂Z¹ or hydroxyl, where                -   Z¹ is hydroxyl or an alkali-detachable group; or    -   D¹ and D² are independently a naphthyl group of the general        formula (2)    -    where        -   R³ and R⁴ are independently hydrogen, (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro,            amido, ureido or halogen; and        -   X² has one of the meanings of X¹; or    -   D¹ and D² are independently a group of the general formula (3)    -    where        -   R⁵ and R⁶ independently have one of the meanings of R¹ and            R²;        -   R⁷ is hydrogen, (C₁-C₄)-alkyl, unsubstituted or            (C₁-C₄)-alkyl-, (C₁-C4)-alkoxy-, sulfo-, halogen- or            carboxyl-substituted phenyl; and        -   Z² is a group of the general formula (4) or (5) or (6)    -    where        -   V is fluorine or chlorine;        -   U¹, U² are independently fluorine, chlorine or hydrogen; and        -   Q¹, Q² are independently chlorine, fluorine, cyanamido,            hydroxyl, (C₁-C₆)-alkoxy, phenoxy, sulfophenoxy, mercapto,            (C₁-C₆)-alkylmercapto, pyridino, carboxypyridino,            carbamoylpyridino or a group of the general formula (7) or            (8)    -    where        -   R⁸ is hydrogen or (C₁-C₆)-alkyl, sulfo-(C₁-C₆)-alkyl or            phenyl unsubstituted or substituted by (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, sulfo, halogen, carboxyl, acetamido, ureido;        -   R⁹ and R¹⁰ independently have one of the meanings of R⁸ or            combine to form a cyclic ring system of the formula            —(CH₂)_(j)—, where j is 4 or 5, or alternatively            —(CH₂)₂-E-(CH₂)₂—, where E is oxygen, sulfur, sulfo, —NR¹¹            where R¹¹═(C₁-C₆)-alkyl;        -   W is phenylene which is unsubstituted or substituted by 1 or            2 substituents, such as (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,            carboxyl, sulfo, chlorine, bromine, or is            (C₁-C₄)-alkylene-arylene or (C₂-C₆)-alkylene, which can be            interrupted by oxygen, sulfur, sulfo, amino, carbonyl,            carboxamido, or is phenylene-CONH-phenylene, which is            unsubstituted or substituted by (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or            halogen, or is naphthylene which is unsubstituted or            substituted by 1 or 2 sulfo groups; and        -   Z is as defined above; or    -   D¹ and D² are independently a group of the general formula (9)    -    where        -   R¹² is hydrogen, (C₁-C₄)-alkyl, aryl or a substituted aryl            radical;        -   R¹³ and R¹⁴ are independently hydrogen, (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro,            amido, ureido or halogen; and        -   A is a phenylene group of the general formula (10)    -    where        -   R¹⁵ and R¹⁶ are independently hydrogen, (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro,            amido, ureido or halogen; or    -   a naphthylene group of the general formula (11)    -    where        -   R¹⁷ and R¹⁸ are independently hydrogen, (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro,            amido, ureido or halogen; or    -   a polymethylene group of the general formula (12)        —(CR¹⁹R²⁰)_(k)—  (12)    -    where        -   k is a whole number greater than 1 and        -   R¹⁹ and R²⁰ are independently hydrogen, (C₁-C₄)-alkyl,            (C₁-C₄)-alkoxy, hydroxyl, cyano, amido, halogen or aryl; and    -   X³ has one of the meanings of X¹; and    -   R, R* are independently hydrogen, (C₁-C₄)-alkyl or sulfomethyl;        and    -   M is hydrogen, an alkali metal or one equivalent of an alkaline        earth metal, with the proviso that the dyes of the general        formulae (I) contain at least one fiber-reactive group of the        general formula (4) or (6).

The individual symbols in the general formulae above and below can haveidentical or different meanings under their definition, irrespective ofwhether the symbols bear the same or a different designation.

(C₁-C₄)-Alkyl R may be straight-chain or branched and is in particularmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl ortert-butyl. Methyl and ethyl are preferred. The same logic applies to(C₁-C₄)-alkoxy groups.

Aryl R is in particular phenyl. Substituted aryl R⁸ to R¹⁰ or R¹² is inparticular phenyl substituted by one, two or three independent groupsselected from the group consisting of (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,hydroxyl, sulfo, carboxyl, amido and halogen.

Halogen R is in particular fluorine, chlorine or bromine, and fluorineand chlorine are preferred.

Alkali-eliminable Z¹ in the β-position of the ethyl group of Z includefor example halogen atoms, such as chlorine and bromine, ester groups oforganic carboxylic and sulfonic acids, as of alkylcarboxylic acids,substituted or unsubstituted benzenecarboxylic acids and substituted orunsubstituted benzenesulfonic acids, such as alkanoyloxy of 2 to 5carbon atoms, especially acetyloxy, benzoyloxy, sulfobenzoyloxy,phenylsulfonyloxy and toluylsulfonyloxy, also acidic ester groups ofinorganic acids, as of phosphoric acid, sulfuric acid and thiosulfuricacid (phosphato, sulfato and thiosulfato groups), similarly dialkylaminogroups having alkyl groups of 1 to 4 carbon atoms in each case, such asdimethylamino and diethylamino.

Z is preferably vinyl, β-chloroethyl and particularly preferablyβ-sulfatoethyl.

The groups “sulfo”, “carboxyl”, “thiosulfato”, “phosphato” and “sulfato”include not only their acid form but also their salt form. Accordingly,sulfo groups are groups conforming to the general formula —SO₃M,thiosulfato groups are groups conforming to the general formula —S—SO₃M,carboxyl groups are groups conforming to the general formula —COOM,phosphato groups are groups conforming to the general formula —OPO₃M₂and sulfato groups are groups conforming to the general formula —OSO₃M,in each of which M is as defined above.

The dyes of the general formula (I) may possess different fiber-reactivegroups —SO₂Z within the meaning of Z. More particularly, thefiber-reactive groups —SO₂Z may be on the one hand vinylsulfonyl groupsand on the other —CH₂CH₂Z¹ groups, preferably β-sulfatoethylsulfonylgroups. If the dyes of the general formula (I) contain vinyl-sulfonylgroups in some instances, then the fraction of the respective dye withthe vinylsulfonyl group is up to about 30 mol %, based on the respectiveamount of total dye.

Alkali M is in particular lithium, sodium or potassium. M is preferablyhydrogen or sodium.

R¹ and R² are preferably hydrogen, (C₁-C₄)-alkyl groups, (C₁-C₄)-alkoxygroups, sulfo or carboxyl and more preferably hydrogen, methyl, methoxyor sulfo.

R³ to R⁵ and R¹² to R²⁰ are preferably hydrogen, R³ to R⁶, R¹⁷ and R¹⁸are also preferably sulfo.

R⁷ to R¹⁰ are preferably hydrogen or methyl, R⁷ and R⁸ are alsopreferably phenyl and R⁹ and R¹⁰ are preferably 2-sulfoethyl, 2-, 3- or4-sulfophenyl or R⁹ and R¹⁰ combine to form a cyclic ring system whichpreferably conforms to the formula —(CH₂)₂—O—(CH₂)₂—.

Examples of groups D¹ and D² of the general formulae (1) and (2) are2-(β-sulfato-ethylsulfonyl)-phenyl, 3-(β-sulfatoethylsulfonyl)-phenyl,4-(β-sulfatoethylsulfonyl)-phenyl,2-carboxy-5-(β-sulfatoethylsulfonyl)-phenyl,2-chloro-4-(β-sulfatoethyl-sulfonyl)-phenyl,2-chloro-5-(β-sulfatoethylsulfonyl)-phenyl,2-bromo-4-(β-sulfato-ethylsulfonyl)-phenyl,2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl,2-sulfo-5-(β-sulfato-ethylsulfonyl)-phenyl,2-methoxy-5-(β-sulfatoethylsulfonyl)-phenyl,2-ethoxy-5-(β-sulfatoethylsulfonyl)-phenyl,2,5-dimethoxy4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-methyl4-(β-sulfatoethylsulfonyl)-phenyl,2-methyl-4-(β-sulfatoethyl-sulfonyl)-phenyl, 2- or 3- or4-(β-thiosulfatoethylsulfonyl)-phenyl,2-methoxy-5-(β-thiosulfatoethylsulfonyl)-phenyl,2-sulfo-4-(β-phosphatoethylsulfonyl)-phenyl, 2- or 3- or4-vinylsulfonyl-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl,2-chloro-4-(β-chloro-ethylsulfonyl)-phenyl,2-chloro-5-(β-chloroethylsulfonyl)-phenyl, 3- or4-(β-acetoxyethylsulfonyl)-phenyl, 6- or8-(β-sulfatoethylsulfonyl)-naphth-2-yl,6-(β-sulfatoethylsulfonyl)-1-sulfo-napth-2-yl and8-(β-sulfatoethylsulfonyl)-6-sulfo-naphth-2-yl, preferably3-(β-sulfatoethylsulfonyl)-phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl,2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-(β-sulfato-ethylsulfonyl)-phenyl,2,5-dimethoxy4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl and 3- or4-vinylsulfonyl-phenyl, or D¹ and D² conform to a group of the generalformula (3) or (9) where R⁵ to R⁷ and R¹² to R¹⁴ have theabove-described preferred meanings.

When D¹ or D² is a group of the general formula (2), the bond whichleads to the diazo group is preferably attached to the naphthalenenucleus in the β-position.

When A is phenylene and X³ is —SO₂Z, the SO₂Z group is preferablydisposed meta or para relative to the nitrogen atom. In the group of thegeneral formula (9), the carboxamide group is preferably disposed paraor meta relative to the diazo group. When A is naphthylene, the bondleading to the nitrogen atom is preferably attached to the naphthalenenucleus in the β-position.

Examples of substituents A are in particular 1,2-phenylene,1,3-phenylene, 1,4-phenylene, 2-chloro-1,4-phenylene,2-chloro-1,5-phenylene, 2-bromo-1,4-phenylene, 2-sulfo-1,4-phenylene,2-sulfo-1,5-phenylene, 2-methoxy-1,5-phenylene, 2-ethoxy-1,5-phenylene,2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene,2-methyl-1,4-phenylene, 2,6-naphthylene, 2,8-naphthylene,1-sulfo-2,6-naphthylene, 6-sulfo-2,8-naphthylene or 1,2-ethylene and1,3-propylene.

A is particularly preferably 1,3-phenylene, 1,4-phenylene,2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene,2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene or1,2-ethylene and 1,3-propylene, and in the case of the twolast-mentioned alkylene groups R¹ is preferably phenyl or 2-sulfophenyl.

k is preferably 2 or 3.

W is preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene,2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene,2-methoxy-5-methyl-1,4-phenylene, 1,2-ethylene, 1,3-propylene.

Examples of the groups Q¹ and Q² in the general formula (5) areindependently fluorine, chlorine, hydroxyl, methoxy, ethoxy, phenoxy,3-sulfophenoxy, 4-sulfophenoxy, methylmercapto, cyanamido, amino,methylamino, ethylamino, morpholino, piperidino, phenylamino,methylphenylamino, 2-sulfophenylamino, 3-sulfophenylamino,4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-disulfophenylamino,2-sulfoethylamino, N-methyl-2-sulfoethylamino, pyridino,3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino,4-carbamoylpyridino, 2-(2-sulfatoethylsulfonyl)-phenylamino,3-(2-sulfatoethylsulfonyl)-phenylamino,4-(2-sulfatoethylsulfonyl)-phenylamino,N-ethyl-3-(2-sulfatoethylsulfonyl)-phenylamino,N-ethyl-4-(2-sulfatoethylsulfonyl)-phenylamino,2-carboxy-5-(2-sulfatoethylsulfonyl)-phenylamino),2-chloro4-(2-sulfatoethylsulfonyl)-phenylamino,2-chloro-5-(2-sulfatoethylsulfonyl)-phenylamino,2-bromo-4-(2-sulfatoethylsulfonyl)-phenylamino,2-sulfo-4-(2-sulfatoethylsulfonyl)-phenylamino,2-sulfo-5-(2-sulfatoethylsulfonyl)phenylamino,2-methoxy-5-(2-sulfatoethylsulfonyl)-phenylamino,2,5-dimethoxy-4-(2-sulfatoethylsulfonyl)-phenylamino,2-methoxy-5-methyl-4-(2-sulfatoethylsulfonyl)-phenylamino,2-methyl-4-(2-sulfatoethylsulfonyl)-phenylamino,2-(vinylsulfonyl)-phenylamino, 3-(vinylsulfonyl)-phenylamino,4-(vinylsulfonyl)-phenylamino, N-ethyl-3-(vinylsulfonyl)-phenylamino,N-ethyl-4-(vinylsulfonyl)-phenylamino,6-(2-sulfatoethylsulfonyl)-naphth-2-ylamino,8-(2-sulfatoethylsulfonyl)-naphth-2-ylamino,8-(2-sulfatoethyl-sulfonyl)-6-sulfo-naphth-2-ylamino,3-(2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenylamino,4-(2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenylamino,3-(2-(vinylsulfonyl)-ethylcarbamoyl)-phenylamino,4-(2-(vinylsulfonyl)-ethylcarbamoyl)-phenylamino,4-(N-methyl-2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenylamino,4-(N-phenyl-2-(2-sulfatoethylsulfonyl)ethylcarbamoyl)phenylamino,4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino,4-(4-(2-sulfatoethyl-sulfonyl)-phenylcarbamoyl)-phenylamino,3-(3-(2-sulfatoethylsulfonyl)-phenyl-carbamoyl)-phenylamino,3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino,3-(2-sulfatoethylsulfonyl)-propylamino,N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino,N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino,N-phenyl-N-(3-(2-sulfatoethylsulfonyl)-propyl)-amino.

Preferably, the groups Q¹ and Q² in the general formula (5) areindependently fluorine, chlorine, cyanamido, morpholino,2-sulfophenylamino, 3-sulfophenyl-amino, 4-sulfophenylamino,N-methyl-2-sulfoethylamino, 3-carboxypyridino, 4-carboxypyridino,3-carbamoylpyridino, 4-carbamoylpyridino,3-(2-sulfatoethyl-sulfonyl)-phenylamino,4-(2-sulfatoethylsulfonyl)-phenylamino, 3-(vinylsulfonyl)-phenylamino,4-(vinylsulfonyl)-phenylamino,4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino,4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino,3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino,3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino,N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino,N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino.

More preferably, the groups Q¹ and Q² in the general formula (5) areindependently fluorine, chlorine, cyanamido, morpholino,2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino,3-(2-sulfatoethylsulfonyl)-phenylamino,4-(2-sulfatoethylsulfonyl)-phenylamino, 3-(vinylsulfonyl)-phenylamino,4-(vinyl-sulfonyl)-phenylamino,N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino,N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino.

Examples of the group Z² are 2,4-difluoro-pyrimidin-6-yl,4,6-difluoro-pyrimidin-2-yl, 5-chloro-2,4-difluoro-pyrimidin-6-yl,5-chloro-4,6-difluoro-pyrimidin-2-yl, 4,5-difluoro-pyrimidin-6-yl,5-chloro4-fluoro-pyrimidin-6-yl, 2,4,5-trichloro-pyrimidin-6-yl,4,5-dichloro-pyrimidin-6-yl, 2,4-dichloro-pyrimidin-6-yl,4-fluoro-pyrimidin-6-yl, 4-chloro-pyrimidin-6-yl, or a group of thegeneral formula (5) having the above-indicated examples of Q¹ and Q² or2,3-dichloroquinoxaline-6-carbonyl.

Preferably, Z² is 2,4-difluoro-pyrimidin-6-yl,4,6-difluoro-pyrimidin-2-yl, 5-chloro-2,4-difluoro-pyrimidin-6-yl,5-chloro-4,6-difluoro-pyrimidin-2-yl or a group of the general formula(5) having the above-indicated preferred groups Q¹ and Q².

More preferably, Z² is 2,4-difluoro-pyrimidin-6-yl,5-chloro-2,4-difluoro-pyrimidin-6-yl or a group of the general formula(5) having the above-indicated particularly preferred groups Q¹ and Q².

Preferred dyes conform to the general formula (Ia)

In the general formula (Ia), D¹, D², M and R have the abovementionedmeanings.

Optionally, the dye mixtures according to the present invention can alsocontain one or more monoazo dyes of the general formulae (13), (14) or(15) in an amount of up to 10% by weight and preferably up to 5% byweight,

where D¹, D², R, R* and M have the abovementioned meanings. Morepreferably, R* is hydrogen.

The dyes according to the invention can be present as a preparation insolid or liquid (dissolved) form. In solid form, they contain, to theextent necessary, the electrolyte salts customary in the case ofwater-soluble and especially fiber-reactive dyes, such as sodiumchloride, potassium chloride and sodium sulfate, and may further containthe auxiliaries customary in commercial dyes, such as buffer substancescapable of setting a pH in aqueous solution between 3 and 7, for examplesodium acetate, sodium citrate, sodium borate, sodium bicarbonate,sodium dihydrogenphosphate and disodium hydrogenphosphate, also dyeingauxiliaries, dustproofing agents and small amounts of siccatives; whenthey are present in a liquid, aqueous solution (including a content ofthickeners of the type customary in print pastes), they may also containsubstances which ensure a long life for these preparations, for examplemold preventatives.

In solid form, the dyes according to the invention are generally presentas powders or granules which contain electrolyte salt and which willhereinbelow generally be referred to as a preparation with or withoutone or more of the abovementioned auxiliaries. In the preparations, thedyes are present at 20 to 90% by weight, based on the preparationcontaining it. The buffer substances are generally present in a totalamount of up to 5% by weight, based on the preparation.

When the dyes according to the invention are present in an aqueoussolution, the total dye content of these aqueous solutions is up toabout 50% by weight, for example between 5 and 50%, the electrolyte saltcontent of these aqueous solutions preferably being below 10% by weight,based on the aqueous solution; the aqueous solutions (liquidpreparations) can contain the aforementioned buffer substances in anamount which is generally up to 5% by weight and preferably up to 2% byweight.

Dyes of the general formulae (13), (14) and (15) are in some instancesformed during the synthesis of dyes of the general formula (I).

The dyes according to the invention are preparable for example by oneequivalent of an amine of the general formula (16)D¹-NH₂   (16),where D¹ is as defined above being diazotized in conventional manner andthe resulting diazonium compound being reacted in a first stage with anaqueous solution or suspension of one equivalent of a coupling componentas per the general formula (17)

where R, R* and M are each as defined above, in an acidic medium to forma monoazo dye as per the general formula (13) and subsequently oneequivalent of an amine of the general formula (18)D²-NH₂   (18),where D² is as defined above, being diazotized in conventional mannerand the resulting diazonium compound being coupled in the second stagewith the monoazo dye of the general formula (13) obtained in the firststage to form the disazo dye of the general formula (I).

When the groups D¹ and D² as per the general formulae (I) have the samemeaning, the preparation can be effected by two equivalents of an amineof the general formula (16) where D¹ is as defined above beingdiazotized in conventional manner and reacted in a first stage in anacidic medium with one equivalent of a coupling component of the generalformula (17) to form a monoazo dye of the general formula (13) and thesecond coupling to the disazo dye of the general formula (I) where thegroups D¹ and D² have the same meaning being carried out subsequently byincreasing the pH.

The dyes of the general formula (I) according to the invention areisolated in a conventional manner by salting out for example with sodiumchloride or potassium chloride or by spray drying or evaporating.

It is similarly possible for the as-synthesized solutions of the dyes ofthe general formula (I) to be directly used as liquid preparations fordyeing, where appropriate after addition of a buffer substance and whereappropriate after concentrating.

Dyes which as well as β-chloroethylsulfonyl or(β-thiosulfatoethylsulfonyl or β-sulfatoethylsulfonyl groups alsocontain vinylsulfonyl groups as reactive radicals can be synthesized notonly starting from appropriately substituted vinylsulfonylanilines ornaphthylamines but also by reaction of a dye mixture where Z isβ-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl with an amount ofalkali required for the desired fraction and converting theδ-substituted ethylsulfonyl groups mentioned into vinylsulfonyl groups.This conversion is effected in a manner familiar to one skilled in theart.

The dyes of the general formula (I) according to the invention haveuseful application properties. They are used for dyeing or printinghydroxyl- and/or carboxamido-containing materials, for example in theform of sheetlike structures, such as paper and leather or of films, forexample composed of polyamide, or in bulk, as for example polyamide andpolyurethane, but especially for dyeing and printing these materials infiber form. Similarly, the as-synthesized solutions of the dyes of thegeneral formula (I) according to the invention can be used directly as aliquid preparation for dyeing, if appropriate after addition of a buffersubstance and if appropriate after concentration or dilution.

The present invention thus also provides for the use of the dyes of thegeneral formula (I) according to the invention for dyeing or printingthese materials, or rather processes for dyeing or printing thesematerials in a conventional manner, by using a dye according to theinvention as a colorant. The materials are preferably employed in theform of fiber materials, especially in the form of textile fibers, suchas woven fabrics or yarns, as in the form of hanks or wound packages.

Hydroxyl-containing materials are those of natural or synthetic origin,for example cellulose fiber materials or their regenerated products andpolyvinyl alcohols. Cellulose fiber materials are preferably cotton; butalso other vegetable fibers, such as linen, hemp, jute and ramie fibers;regenerated cellulose fibers are for example staple viscose and filamentviscose and also chemically modified cellulose fibers, such as aminatedcellulose fibers or fibers as described for example in WO 96/37641 andWO 96/37642 and also in EP-A-0 538 785 and EP-A-0 692 559.

Carboxamido-containing materials are for example synthetic and naturalpolyamides and polyurethanes, especially in the form of fibers, forexample wool and other animal hairs, silk, leather, nylon-6,6, nylon-6,nylon-11 and nylon-4.

The dyes of the general formula (I) according to the invention can beapplied to and fixed on the substrates mentioned, especially the fibermaterials mentioned, by the application techniques known forwater-soluble dyes and especially for fiber-reactive dyes. For instance,on cellulose fibers they produce by the exhaust method from a longliquor and also from a short liquor, for example in a liquor to goodsratio of 5:1 to 100:1, preferably 6:1 to 30:1, using variousacid-binding agents and optionally neutral salts as far as necessary,such as sodium chloride or sodium sulfate, dyeings having very goodcolor yields. Application is preferably from an aqueous bath attemperatures between 40 and 105° C., optionally at a temperature of upto 130° C. under superatmospheric pressure, but preferably at 30 to 95°C., especially 45 to 65° C., in the presence or absence of customarydyeing auxiliaries. One possible procedure here is to introduce thematerial into the warm bath and to gradually heat the bath to thedesired dyeing temperature and complete the dyeing process at thattemperature. The neutral salts which accelerate the exhaustion of thedyes may also if desired only be added to the bath after the actualdyeing temperature has been reached.

Padding processes likewise provide excellent color yields and a verygood color build-up on cellulose fibers, the dyes being fixable in aconventional manner by batching at room temperature or elevatedtemperature, for example at up to 60° C., or in a continuous manner, forexample by means of a pad-dry-pad steam process, by steaming or usingdry heat.

Similarly, the customary printing processes for cellulose fibers, whichcan be carried out in one step, for example by printing with a printpaste containing sodium bicarbonate or some other acid-binding agent andby subsequent steaming at 100 to 103° C., or in two steps, for exampleby printing with a neutral to weak acidic print color and then fixingeither by passing the printed material through a hotelectrolyte-containing alkaline bath or by overpadding with an alkalineelectrolyte-containing padding liquor and subsequent batching of thealkali-overpadded material or subsequent steaming or subsequent dry heattreatment of the alkali-overpadded material, produce strong prints withwell-defined contours and a clear white ground. The outcome of theprints is little affected, if at all, by variations in the fixingconditions.

When fixing by means of dry heat in accordance with the customarythermofix processes, hot air at 120 to 200° C. is used. In addition tothe customary steam at 101 to 103° C., it is also possible to usesuperheated steam and high-pressure steam at temperatures of up to 160°C.

The acid-binding agents which effect the fixation of the dyes of thegeneral formula (I) according to the invention on the cellulose fibersare for example water-soluble basic salts of alkali metals and likewisealkaline earth metals of inorganic or organic acids or compounds whichliberate alkali in the heat, and also alkali metal silicates. Especiallysuitable are the alkali metal hydroxides and alkali metal salts of weakto medium inorganic or organic acids, the preferred alkali metalcompounds being the sodium and potassium compounds. Such acid-bindingagents are for example sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium bicarbonate, potassium carbonate, sodium formate,sodium dihydrogenphosphate, disodium hydrogenphosphate, sodiumtrichloroacetate, trisodium phosphate waterglass or mixtures thereof,for example mixtures of aqueous sodium hydroxide solution andwaterglass.

The dyes of the general formula (I) according to the invention arenotable for outstanding color strength when applied to the cellulosefiber materials by dyeing or printing in the presence of no or verysmall amounts of alkali or alkaline earth metal compounds. For instance,no electrolyte salt is required for a shallow depth of shade, not morethan 5 g/l of electrolyte salt is required for a medium depth of shadeand not more than 10 g/l of electrolyte salt is required for deepshades.

According to the invention, a shallow depth of shade refers to the useof 2% by weight of dye based on the substrate to be dyed, a medium depthof shade refers to the use of 2 to 4% by weight of dye based on thesubstrate to be dyed and a deep shade refers to the use of 4 to 10% byweight of dye based on the substrate to be dyed.

The dyeing and prints obtainable with the dyes of the general formula(I) according to the invention possess bright shades; more particularly,the dyeings and prints on cellulose fiber materials possess goodlightfastness and especially good wetfastnesses, such as fastness towashing, milling, water, seawater, crossdyeing and acidic and alkalineperspiration, also good fastness to pleating, hotpressing and rubbing.Furthermore, the cellulose dyeings obtained following the customaryaftertreatment of rinsing to remove unfixed dye portions exhibitexcellent wetfastnesses, in particular since unfixed dye portions areeasily washed off because of their good solubility in cold water.

Furthermore, the dyes of the general formula (I) according to theinvention can also be used for the fiber-reactive dyeing of wool.Moreover, wool which has been given a nonfelting or low-felting finish(cf. for example H. Rath, Lehrbuch der Textilchemie, Springer-Verlag,3rd edition (1972), pages 295-299, especially finished by the Hercoseftprocess (page 298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975,33-44), can be dyed to very good fastness properties. The process ofdyeing on wool is here carried out in a conventional manner from anacidic medium. For instance, acetic acid and/or ammonium sulfate oracetic acid and ammonium acetate or sodium acetate can be added to thedyebath to obtain the desired pH. To obtain a dyeing of acceptablelevelness, it is advisable to add a customary leveling agent, forexample a leveling agent based on a reaction product of cyanuricchloride with three times the molar amount of an aminobenzenesulfonicacid and/or of an aminonaphthalenesulfonic acid or on the basis of areaction product of for example stearylamine with ethylene oxide. Forinstance, the dye of the general formula (I) according to the inventionis preferably subjected to the exhaust process initially from an acidicdyebath having a pH of about 3.5 to 5.5 under pH control and the pH isthen, toward the end of the dyeing time, shifted into the neutral andoptionally weakly alkaline range up to a pH of 8.5 to bring about,especially for very deep dyeings, the full reactive bond between thedyes and the fiber. At the same time, the dye portion not reactivelybound is removed.

The procedure described herein also applies to the production of dyeingson fiber materials composed of other natural polyamides or of syntheticpolyamides and polyurethanes. In general, the material to be dyed isintroduced into the bath at a temperature of about 40° C., agitatedtherein for some time, the dyebath is then adjusted to the desiredweakly acidic, preferably weakly acetic acid, pH and the actual dyeingis carried out at a temperature between 60 and 98° C. However, thedyeings can also be carried out at the boil or in sealed dyeingapparatus at temperatures of up to 106° C. Since the water solubility ofthe dyes of the general formula (I) according to the invention is verygood, they can also be used with advantage in customary continuousdyeing processes. The color strength of the dyes according to theinvention is very high.

The dyes of the general formula (I) according to the invention dye thematerials mentioned, preferably fiber materials, in yellowish tobrownish red shades having good fastness properties.

The examples hereinbelow serve to illustrate the invention. Parts andpercentages are by weight, unless otherwise stated. Parts by weightrelate to parts by volume as the kilogram relative to the liter. Thecompounds described in the examples in terms of a formula are indicatedin the form of the free acids, since they are generally prepared andisolated in the form of their salts, preferably sodium or potassiumsalts, and used for dyeing in the form of their salts. The startingcompounds described in the examples hereinbelow, especially the tableexamples, can be used in the synthesis in the form of the free acid orlikewise in the form of their salts, preferably alkali metal salts, suchas sodium or potassium salts. The reported UV/Vis absorption maxima weredetermined in water as a solvent.

EXAMPLE 1

a) 302 parts of the product obtained by condensation of 134 parts of2,4,6-trifluoro-pyrimidine with 188 parts of 2 4-diaminobenzenesulfonicacid are suspended in 2 500 parts of ice-water and 350 parts of 30%hydrochloric acid and diazotized at 5° C. by dropwise addition of 175parts of 40% sodium nitrite solution. After the excess nitrite has beenremoved with sulfamic acid, 333 parts are added of4-hydroxy-7-(sulfomethyl-amino)-naphthalene-2-sulfonic acid, prepared byreaction of 239 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acidwith 147 parts of formaldehyde sodium bisulfite in an aqueous medium atpH 5.5-6 and 40-50° C., and a coupling reaction is carried out at 5-10°C. and below pH 1.5 to form a reddish orange monoazo dye of the formula(13-1).

b) In a second, separate reaction vessel, 281 parts of4-(β-sulfatoethylsulfonyl)-aniline are suspended in 700 parts ofice-water and 180 parts of 30% hydrochloric acid and diazotized bydropwise addition of 174 parts of 40% sodium nitrite solution.Subsequently the excess nitrite is removed with sulfamic acid solutionand the diazo suspension obtained is pumped after the first coupling hasended into the solution of the monoazo dye (13-1) of a) while at thesame time pH 5-6 is set and contained with sodium carbonate at below 25°C.

The yellowish red disazo dye of the formula (I-1) which is formed afterthe second coupling reaction has ended can be isolated by spray dryingor evaporating under reduced pressure or by salting out with sodiumchloride or potassium chloride.

Alternatively, the dye solution obtained can also be buffered at pH5.5-6 by addition of a phosphate buffer and be adjusted by furtherdilution or concentration to provide a liquid brand of defined strength.

The dye obtained, which is according to the invention, dyes cotton inyellowish red shades having good general fastnesses.

EXAMPLE 2

a) 361 parts of 2-amino-5-(β-sulfatoethylsulfonyl)-benzenesulfonic acidare suspended in a mixture of 1 500 parts of water and 300 parts ofconcentrated sulfuric acid and diazotized at 10° C. by dropwise additionof 175 parts of 40% sodium nitrite solution. After the excess nitritehas been removed with sulfamic acid 239 parts are added of7-amino-4-hydroxy-naphthalene-2-sulfonic acid in the form of an aqueoussolution (pH 6.5-7) and a coupling reaction is carried out at 5-10° C.and below pH 1.3 to form a red monoazo dye of the formula (13-2).

b) In a second, separate reaction vessel, 302 parts of the productobtained by condensation of 134 parts of 2,4,6-trifluoro-pyrimidine with180 parts of 2,4-diaminobenzenesulfonic acid are suspended in 3 000parts of water and admixed with 175 parts of 40% sodium nitritesolution. This mixture is added dropwise to an initial charge of 1 000parts of ice and 330 parts of 30% hydrochloric acid and the batch issubsequently stirred at 10° C. until diazotization is complete.Subsequently the excess nitrite is removed with sulfamic acid solutionand the diazo suspension obtained is pumped after the first coupling hasended into the solution of the monoazo dye (13-2) of a) while at thesame time pH 5-6 is set and maintained with sodium carbonate at below15° C.

The yellowish red disazo dye of the formula (1-2) formed after thesecond coupling reaction has ended can be isolated by evaporation underreduced pressure, where appropriate after the reaction solution has beendemineralized. The dye obtained, which is according to the invention,dyes cotton in yellowish red shades having good general fastnesses.

EXAMPLE 3

336.5 parts of the product obtained by condensation of 168.5 parts of5-chloro-2,4,6-trifluoro-pyrimidine with 188 parts of2,4-diaminobenzenesulfonic acid are diazotized similarly to example 1a)or 2b) and, after removal of the excess nitrite with sulfamic acid,admixed with 166.5 parts of4-hydroxy-7-(sulfomethyl-amino)-naphthalene-2-sulfonic acid (prepared byreaction of 119.5 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acidwith 74 parts of formaldehyde sodium bisulfite in an aqueous medium atpH 5.5-6 and 40-50° C) and coupled in a first stage at 5-10° C. andbelow pH 1.5 to form a reddish orange monoazo dye of the formula (13-3).

After the first coupling to the monoazo dye (13-3) has ended, pH 5-6 isset with sodium carbonate at below 25° C. and maintained with sodiumcarbonate until the second coupling reaction has ended. The resultingyellowish red disazo dye of the formula (I-3) can be isolated byevaporation under reduced pressure. The dye obtained, which is accordingto the invention, dyes cotton in yellowish red shades having goodgeneral fastnesses.

EXAMPLES 4 TO 70

The table examples hereinbelow describe further dyes of the generalformula (Iaa) according to the invention. The dyes provide yellowish tobrown red dyeings, on cotton for example, that have good generalfastnesses by the dyeing methods customary for reactive dyes.

Dyes as per example 1 or 2 Example D¹ D² R 4

CH₂—SO₃H 5

CH₂—SO₃H 6

CH₂—SO₃H 7

H 8

H 9

H 10

CH₂—SO₃H 11

H 12

CH₂—SO₃H 13

CH₂—SO₃H 14

H 15

CH₂—SO₃H 16

CH₂—SO₃H 17

CH₂—SO₃H 18

CH₂—SO₃H 19

CH₂—SO₃H 20

H 21

H 22

CH₂—SO₃H 23

CH₂—SO₃H 24

H 25

H 26

CH₂—SO₃H 27

H 28

H 29

CH₂—SO₃H 30

H 31

CH₂—SO₃H 32

CH₂—SO₃H 33

CH₂—SO₃H 34

CH₂—SO₃H 35

CH₂—SO₃H 36

CH₂—SO₃H 37

H 38

H 39

CH₂—SO₃H 40

CH₂—SO₃H 41

CH₂—SO₃H 42

CH₂—SO₃H 43

CH₂—SO₃H 44

CH₂—SO₃H 45

H 46

H 47

CH₂—SO₃H 48

H 49

CH₂—SO₃H 50

H 51

CH₂—SO₃H 52

CH₂—SO₃H 53

H 54

H 55

H 56

H 57

CH₂—SO₃H 58

CH₂—SO₃H 59

H 60

CH₂—SO₃H 61

CH₂—SO₃H 62

CH₂—SO₃H 63

H 64

H 65

CH₂—SO₃H 66

CH₂—SO₃H 67

H 68

CH₂—SO₃H 69

H 70

CH₂—SO₃H

EXAMPLES 71 TO 82

The table examples hereinbelow describe further dyes of the generalformula (Iab) according to the invention. The dyes provide yellowish tobrown red dyeings, on cotton for example, that have good generalfastnesses by the dyeing methods customary for reactive dyes. (lab)

Dyes as per example 3: Example D¹ = D² R 71

CH₂—SO₃H 72

H 73

CH₂—SO₃H 74

CH₂—SO₃H 75

H 76

CH₂—SO₃H 77

H 78

CH₂—SO₃H 79

H 80

H 81

CH₂—SO₃H 82

H

USE EXAMPLE 1

2 parts of a dye obtained according to example 1-3 and 50 parts ofsodium chloride are dissolved in 999 parts of water and 5 parts ofsodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5%aqueous solution) and optionally 1 part of a wetting agent are added.The dyebath is entered with 100 g of a cotton fabric. The temperature ofthe dyebath is first maintained at 25° C. for 10 minutes, then raisedover 30 minutes to the final temperature (40-80° C.) and maintained atthat level for a further 60-90 minutes. Thereafter, the dyed material isrinsed initially with tap water for 2 minutes and then with ion-freewater for 5 minutes. The dyed material is neutralized at 40° C. in 1 000parts of an aqueous solution containing 1 part of 50% acetic acid for 10minutes. It is subsequently rinsed with ion-free water at 70° C. andthereafter soaked off at the boil with a detergent for 15 minutes,rinsed once more and dried. This gives a strong yellowish to brownishred dyeing having very good fastness properties.

USE EXAMPLE 2

2 parts of a dye obtained as per example 3, 43, 44, 47, 48 or 68 aredissolved in 999 parts of water and 5 parts of sodium carbonate, 0.7part of sodium hydroxide (in the form of a 32.5% aqueous solution) andoptionally 1 part of a wetting agent are added. This dyebath is enteredwith 100 g of a cotton fabric. The rest of the processing is asindicated in use example 1. This gives a strong yellowish to brownishred dyeing having very good fastness properties.

USE EXAMPLE 3

4 parts of a dye obtained as per example 3, 43, 44, 47, 48 or 68 and 5parts of sodium chloride are dissolved in 999 parts of water, 7 parts ofsodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5%aqueous solution) and optionally 1 part of a wetting agent are added.This dyebath is entered with 100 g of a cotton fabric. The rest of theprocessing is as indicated in use example 1. This gives a strongyellowish to brownish red dyeing having very good fastness properties.

USE EXAMPLE 4

8 parts of a dye obtained as per example 3, 43, 44, 47, 48 or 68 and 10parts of sodium chloride are dissolved in 997 parts of water, 10 partsof sodium carbonate, 1.3 part of sodium hydroxide (in the form of a32.5% aqueous solution) and optionally 1 part of a wetting agent areadded. This dyebath is entered with 100 g of a cotton fabric. The restof the processing is as indicated in use example 1. This gives a strongyellowish to brownish red dyeing having very good fastness properties.

1. Reactive dyes as per the hereinbelow indicated and defined generalformula (I),

where D¹ and D² are independently a group of the general formula (1)

 where R¹ and R² are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureidoor halogen; and X¹ is hydrogen or a group of the formula —SO₂-Z, where Zis —CH═CH₂, —CH₂CH₂Z¹ or hydroxyl, where Z¹ is hydroxyl or analkali-detachable group; or D¹ and D² are independently a naphthyl groupof the general formula (2)

 where R³ and R⁴ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureidoor halogen; and X² has one of the meanings of X¹; or D¹ and D² areindependently a group of the general formula (3)

 where R⁵ and R⁶ independently have one of the meanings of R¹ and R²; R⁷is hydrogen, (C₁-C₄)-alkyl, unsubstituted or (C₁-C₄)-alkyl-,(C₁-C₄)-alkoxy-, sulfo-, halogen- or carboxyl-substituted phenyl; and Z²is a heterocyclic reactive radical; or D¹ and D² are independently agroup of the general formula (9)

 where R¹² is hydrogen, (C₁-C₄)-alkyl, aryl or a substituted arylradical; R¹³ and R¹⁴ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureidoor halogen; and A is a phenylene group of the general formula (10)

 where R¹⁵ and R¹⁶ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureidoor halogen; or a naphthylene group of the general formula (11)

 where R¹⁷ and R¹⁸ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureidoor halogen; or a polymethylene group of the general formula (12)—(CR¹⁹R²⁰)_(k)—  (12)  where k is a whole number greater than 1 and R¹⁹and R²⁰ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,hydroxyl, cyano, amido, halogen or aryl; and X³ has one of the meaningsof X¹; and R, R* are independently hydrogen, (C₁-C₄)-alkyl orsulfomethyl; and M is hydrogen, an alkali metal or one equivalent of analkaline earth metal, with the proviso that the dyes of the generalformulae (I) contain at least one fiber-reactive heterocyclic group ofthe general formula.
 2. Reactive dyes as per claim 1, wherein Z² is agroup of the general formula (4) or (5) or (6)

 where V is fluorine or chlorine; U¹, U² are independently fluorine,chlorine or hydrogen; and Q¹, Q² are independently chlorine, fluorine,cyanamido, hydroxyl, (C₁-C₆)-alkoxy, phenoxy, sulfophenoxy, mercapto,(C₁-C₆)-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or agroup of the general formula (7) or (8)

 where R⁸ is hydrogen or (C₁-C₆)-alkyl, sulfo-(C₁-C₆)-alkyl or phenylunsubstituted or substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, sulfo,halogen, carboxyl, acetamido, ureido; R⁹ and R¹⁰ independently have oneof the meanings of R⁸ or combine to form a cyclic ring system of theformula —(CH₂)_(j)—, where j is 4 or 5, or alternatively—(CH₂)₂-E-(CH₂)₂—, where E is oxygen, sulfur, sulfo, —NR¹¹ whereR¹¹═(C₁-C₆)-alkyl; W is phenylene which is unsubstituted or substitutedby 1 or 2 substituents, wherein said 1 or 2 substitutents are(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, carboxyl, sulfo, chlorine, bromine, or is(C₁-C₄)-alkylene-arylene or (C₂-C₆)-alkylene, which is optionallyinterrupted by oxygen, sulfur, sulfo, amino, carbonyl, carboxamido, oris phenylene-CONH-phenylene, which is unsubstituted or substituted by(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureidoor halogen, or is naphthylene which is unsubstituted or substituted by 1or 2 sulfo groups; and Z is as defined above.
 3. Reactive dyes as perclaim 1, where the substituents R are hydrogen or sulfomethyl and R* ishydrogen.
 4. Reactive dyes as per claim 1, characterized in that thesubstituents R¹ and R² are hydrogen, methyl, methoxy or sulfo, R¹² toR¹⁶ are hydrogen and R³ to R⁶, R¹⁷ and R¹⁸ are hydrogen or sulfo R⁷ andR⁸ are hydrogen methyl or phenyl and R⁹ and R¹⁰ are hydrogen, methyl2-sulfoethyl, 2-, 3- or 4-sulfophenyl, or R⁹ and R¹⁰ combine to form acyclic ring system which conforms to the formula —(CH₂)₂—O—(CH₂)₂—. 5.Reactive dyes as per claim 1, characterized in that Z is vinyl,β-chloroethyl or β-sulfatoethyl.
 6. Reactive dyes as claimed in claim 2,characterized in that Q¹ and Q² in the general formula (5) areindependently fluorine, chlorine, cyanamido, morpholino,2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino,3-(2-sulfatoethylsulfonyl)phenylamino,4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino,4-(vinylsulfonyl)phenylamino,N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino orN-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino.
 7. A process forpreparing dyes of the general formula (I) as per claim 1, whichcomprises diazotizing one equivalent of an amine of the general formula(16)D¹-NH₂   (16), where D is as defined in claim 1 and the resultingdiazonium compound being reacted in a first stage with an aqueoussolution or suspension of one equivalent of a coupling component as perthe general formula (17)

where R, R* and M are each as defined in claim 1, to form a monoazo dyeas per the general formula (13)

and subsequently one equivalent of an amine of the general formula (18)D²-NH₂   (18), where D² is as defined in claim 1, being diazotized andthe resulting diazonium compound being coupled in the second stage withthe monoazo dye of the general formula (13) obtained in the first stageto form the disazo dye of the general formula (I).
 8. The process forpreparing dyes of the general formula (I) as per claim 1 in the eventthat the groups D¹ and D² as per the general formulae (I) have the samemeaning by two equivalents of an amine of the general formula (16) whereD¹ is as defined in claim 1 which comprises diazotizing and reacting ina first stage with one equivalent of a coupling component of the generalformula (17)

to form a monoazo dye of the general formula (13)

and the second coupling to the disazo dye of the general formula (I)where the groups D¹ and D² have the same meaning being carried outsubsequently.
 9. An aqueous liquid preparation containing a dye as setforth in claim 1 at a level of 5-90% by weight.
 10. (canceled) 11.Reactive dyes as per claim 2, where the substituents R are hydrogen orsulfomethyl and R* is hydrogen.
 12. Reactive dyes as per claim 11,characterized in that the substituents R¹ and R² are hydrogen, methyl,methoxy or sulfo, R¹² to R¹⁶ are hydrogen and R³ to R⁶, R¹⁷ and R¹⁸ arehydrogen or sulfo, R⁷ and R⁸ are hydrogen methyl or phenyl and R⁹ andR¹⁰ are hydrogen, methyl 2-sulfoethyl, 2-, 3- or 4-sulfophenyl, or R⁹and R¹⁰ combine to form a cyclic ring system which conforms to theformula —(CH₂)₂—O—(CH₂)₂—.
 13. Reactive dyes as per claim 12,characterized in that Z is vinyl, β-chloroethyl or β-sulfatoethyl. 14.Reactive dyes as claimed in claim 13, characterized in that Q¹ and Q² inthe general formula (5) are independently fluorine, chlorine, cyanamido,morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino,3-(2-sulfatoethylsulfonyl)phenylamino,4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino,4-(vinylsulfonyl)phenylamino,N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino orN-phenyl-N-(2-(2-sulfatoethyl-sulfonyl)ethyl)amino.
 15. A process ofdyeing or printing hydroxyl- and/or carboxamido-containing fibermaterial which comprises contacting the reactive dyes as per claim 1with said material.